Journal of Geochemical Exploration 92 (2007) 97 110 www.elsevier.

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Mineralogical and geochemical study of element mobility at the sulfide-rich Excelsior waste rock dump from the polymetallic ZnPb(AgBiCu) deposit, Cerro de Pasco, Peru
Jochen Smuda a,d,, Bernhard Dold a,1 , Kurt Friese b,2 , Peter Morgenstern c,3 , Walter Glaesser d,4
c

Centre d'Analyse Minrale, Anthropole, University of Lausanne, 1015 Lausanne, Switzerland UFZ-Umweltforschungszentrum, Department Lake Research, Brueckstr. 3a, D-39114 Magdeburg, Germany UFZ-Umweltforschungszentrum, Department Chemical Analytic, Permoserstrae 15, D-04303 Leipzig, Germany d University of Leipzig, Institute of Geophysics and Geology, Talstr. 35, D-04211 Leipzig, Germany
b

Accepted 8 August 2006 Available online 2 October 2006

Abstract We present a mineralogical and geochemical study of the sulfide-rich waste rock dump Excelsior (size: 94 ha) originating from the Cerro de Pasco mine (altitude: 4300 m a.s.l.), Central Andes, Peru. The aims of this study were: to characterise (1) the secondary mineral assemblage and (2) the acid mine drainage (AMD) from this waste rock dump. (3) This information was used to create a model of the element transport in and out of the waste rock dump under the highly variable mountain climate with high precipitation during the wet season and high evaporation during the dry season. The main ore minerals found in the polymetallic PbZn(AgBiCu) deposit are pyrite, sphalerite, galena and enargite with minor finds of tennantite, covellite and cerrusite. Gangue was dominantly quartz hematite siderite muscovite. The waste rocks had a high potential of acid generation with low neutralization potential (estimated N 60 wt.% pyrite, b 5 wt.% calcite/dolomite) with an already acidic environment (average paste pH 2.8). Gypsum, different types of jarosite and a variety of Fe-sulfates (e.g. melanterite (Fe(SO4)7H2O) and rozenite (Fe(SO4)4H2O)) were the dominant secondary minerals. Less frequent secondary minerals were: Fe(III)-hydroxides (schwertmannite (Fe16O16(OH)12(SO4)2), fibroferrite (Fe(SO4)(OH)5H2O)), and Mg-, Mn- and Zn-sulfates (e.g. starkeyite (Mg(SO4)4H2O), mallardite (Mn(SO4)7H2O), goslarite (Zn(SO4)7H2O), respectively). For the primary mineral assemblage, X-ray fluorescence analyses displayed average concentrations of the heavy metals: Cu 0.1 wt.%, Zn 1.1 wt.%, Pb 1.2 wt.% and Cd 40 mg/kg and of the metalloid As 0.15 wt.%. In secondary minerals an average enrichment of Cu: 0.8 wt.%, Zn: 2.9 wt.%, As: 0.27 wt.% and Cd: 71 mg/kg was observed. Effects of rain events on the waste rocks were simulated by water-leach tests of (1) solid samples from the top, representing waste rocks leached by infiltrating rainwater and (2) solid samples around the base, representing waste rocks affected by outcropping AMD generated in the waste rock dump. The leachates showed stored acidity (pH 1.25.6 of the leachates) and high solubility of secondary minerals (average electrical conductivity: 9.7 mS/cm and average concentrations for Fe: 928 mg/L, Zn: 315 mg/L, Cu: 7.5 mg/L, As: 4.1 mg/L, Cd: 1.59 mg/L, and Pb: 0.31 mg/L). The AMD
Corresponding author. Centre d'Analyse Minrale, Anthropole, University of Lausanne, 1015 Lausanne, Switzerland. Fax: +41 21 692 4315. E-mail addresses: Jochen.Smuda@unil.ch (J. Smuda), Bernhard.Dold@unil.ch (B. Dold), Kurt.Friese@ufz.de (K. Friese), Peter.Morgenstern@ufz.de (P. Morgenstern), Walter.Glaesser@ufz.de (W. Glaesser). 1 Tel./fax: +41 21 692 4324. 2 Tel./fax: +49 391 8109 150. 3 Tel./fax: +49 341 235 2625. 4 Tel./fax: +49 341 973 2809. 0375-6742/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.gexplo.2006.08.001

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output at springs at the base of the waste rock dump is chemically similar to the leachates (acidic pH (2.785.10), oxidizing Eh (319 684 mV)), but higher charged with maximum concentrations for Fe: 5640 mg/L, Zn: 3000 mg/L, Cu: 161 mg/L, As: 8.0 mg/L, Cd: 6.6 mg/L, and with higher electrical conductivity (1926 mS/cm). The data suggest that AMD formation is strongly controlled by the local climate. During the dry winter season, high evaporation of outcropping pore solutions and subsequently precipitation of efflorescent salts resulted in a heavy metal-enrichment at the base of the Excelsior waste rock dump. During the wet summer season, rain events caused the dissolution of most efflorescent salts, removed the enrichment at the base and resulted in a washout of acid solutions rich in Fe, Mn, Zn, Cu, Cd, As and S. 2006 Elsevier B.V. All rights reserved.
Keywords: Acid mine drainage; Waste rock dump; Climate; Efflorescent salts; Heavy metal-sulfates; Leach test

1. Introduction Sulfidic mine waste dumps are an important source of metal contamination in the mining environment. While acid mine drainage (AMD) in mine tailings has been studied extensively (e.g. Jambor, 1994; Dold and Fontbot, 2001), there are still few works on the subject of AMD formation in sulphidic waste rock dumps. Sracek et al., 2004, studied AMD and secondary minerals from a waste rock dump with a low pyrite content. They pointed out that physical and geochemical processes within a waste rock dump are interconnected and depend strongly on climate, waste rock texture and stability. Recently, the importance of climate for the AMD generation due to formation and dissolution of watersoluble secondary minerals at mining sites has been recognised. Gier et al. (2003) studied the role of secondary mineralogy in the control of the migration of heavy metals and As at a relatively small sulfide-rich waste rock dump in Russia. Beside a characterisation of the secondary mineral assemblage of sulfidic waste dumps, their analyses of climatic influences on the secondary minerals suggested that AMD output is strongly controlled by rain events. Frau (2000) reported that highly water-soluble secondary melanterite from pyrite alteration can store acidity and heavy metals during dry seasons which are then released due to the dissolution of this mineral during wet seasons. We studied a sulfide-rich waste rock dump at the elevated plain of the Central Andes of Peru to characterise these secondary minerals, their water-solubility and the element outflow from this waste rock dump under the high precipitationhigh evaporation mountain climate. Water-leach tests are useful to simulate rain events and evaluate the solubility of secondary minerals and the element/acid liberation. Hammarstrom et al. (2005) showed with this type of leach tests that efflorescent salts from different mining waste locations in the eastern US dissolve easily in water, producing acidic, metal-

loaded solutions. In this study, we focused on differences between solid samples and leachates from samples from the upper terraces of the waste rock dump and from samples from its base. The geochemical and mineralogical differences between these samples were used to evaluate water pathways and effects of the climate on element transport and fixation. Geochemical data from the outcropping AMD displayed the subsequent transport of elements out of the waste rock dump system. 2. Description of the studied waste rock dump The open pit and underground mine of Cerro de Pasco (Volcan Corporation S.A.A.) is located in the Sierra Central of Peru at an altitude of 4300 m above sea terrace (Fig. 1A). Since the 16th century, Cu and Ag have been exploited from the Cerro de Pasco ore body. In 1963, the exploitation moved to PbZnAg. The studied Excelsior waste rock dump operated from 1943 until 2000 initially as a dump for rocks with non-economic Cu and later for non-economic Zn and Pb concentrations. The waste rock dump is located in the SW of the mine in the bottom of a valley and occupies an area of 94 ha, containing 26,400,000 m3 of broken rocks. It partly overlies the downstream Quiulacocha tailings impoundment (ca. 60 ha covered, 114 ha not covered). The bedrock of the deposition zone consists of Devonian phyllites and shales with low hydraulic conductivity. 2.1. Ore and regional geology The polymetallic ZnPb(AgBiCu) Cerro de Pasco deposit represents an economically vital polymetallic source with an estimated total amount of 100 Mt at about 7 wt.% Zn, 2 wt.% Pb and 3 oz/t Ag (Baumgartner et al., 2003). Hydrothermal solutions associated with volcanic activity formed as the first stage of sulfide deposition an extensive replacement body of quartzpyrite in TriassicJurassic limestone/

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Fig. 1. (A) Location and geological setting of the Cerro de Pasco mine area, Peru. (B) Topographical map of the Excelsior waste rock dump with the sampling points.

dolomite which represents 90 vol.% of the entire ore body (Einaudi, 1977). At the contact zone between the host rock and the quartzpyrite body, carbonates of the host rock formation were altered to ankerite and siderite. Tertiary volcanic rocks (quartz monzonite/tuff) which partially overlaid the host rock formation were altered in contact with this quartzpyrite body to muscovite quartzpyrite. The second stage of sulfide deposition formed the main ZnPb ore in the form of pipes with dominantly sphaleritegalena and minor tennantite, marmantite and chalcopyrite. Veins rich in enargite, luzonite, galena and minor tennantite represent a third stage of sulfide deposition. The final hydrothermal activity resulted in local leaching and formation of a mineral assemblage of pyritehematiterealgar associated with a high Ag-mineralization. The oxidation of the top of the sulfide body formed a gossan which contains quartz and hematite/goetite as major phases (Petersen, 1965).

2.2. Mining and deposition processes The waste rocks deposited at the Excelsior waste rock dump had an average size of 10 cm and are up to 2.5 m in diameter; the fraction of grains smaller than 2 mm were estimated as about 10 vol.%. The waste rock impoundment consisted of three terraces constructed by the downpour of fractured rocks at the slopes of the different terraces with an uncontrolled mixing of different rock types. As result, cross-bedding of the waste rocks and a gradation of rocks with big boulders at the base and fine grain material at the top were observed (Fig. 2A). The deposition commenced in the northern part with waste rocks from the Cu-ore and advanced with the later deposition of waste rocks from the ZnPb ore successively to the south and from the 1st terrace to the 3rd terrace, respectively. The northern part and lower terraces were therefore exposed to alteration for a longer period than the southern parts and the top terrace. The

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Fig. 2. Schematic cross-section of the Excelsior waste rock dump: (A) structure; (B) main water pathways.

surfaces of the terraces were mainly floored with a 10 to 30 cm thick cover of rugged pyrite-rich waste rocks to prevent heavy mine equipment from getting stuck. The maximum height of the dump is 55 m; the slope inclination is mainly between 33 and 36. 2.3. Climate and hydrology Based on data from the local meteorological stations (Cerro de Pasco and Upamayo), the climate at Excelsior waste rock dump is characterised by an average precipitation of 1025 mm/year (mainly in the summer period), an average evaporation of 988 mm/year and an average annual temperature of 4.2 C.

The hydrological system of the Excelsior waste rock dump received water mainly from rain. Two water pathways were observed in the waste dump (Fig. 2B): (1) Surface run-off at the waste dump slopes after rain events; and (2) water infiltration into the dump. In the waste rock dump, the main direction of water infiltration was suggested to be vertical. At different positions of the waste rock dump, base material was removed which formed overhangs. It was observed that the precipitation of efflorescent salts at these outcrops was favoured at discrete cross-bedding layers (Fig. 3). This observation suggested a certain influence on the water infiltration by the cross-bedding. A broad spring zone existed at the south-western limit of the Excelsior waste rock dump

Fig. 3. Outcrop at the south-western base of the Excelsior waste rock dump (sampling point CPE-30, Fig. 1B) with efflorescent salts (melanterite; ES sample) and oxidizing primary rocks (pyrite, volcanic rocks; AR sample). The preferential formation of ES stalactites at grain-size boundaries suggested the control of solution flow by the cross-bedding in the waste rock dump.

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(water sampling points CPE-W1-3, Fig. 1B). These water outcrops were explained by the difference of hydraulic permeability between the coarse waste rock dump material (high water permeability, not water saturated) and the underlying sandy/silty tailings material (low water permeability, water saturated). Similar to an aquitard, the underlying tailings impoundment seemed to retard infiltration through its fine material. This led to a horizontal water transport with spring-like outcrops at the southern base of the dump. The AMD from the springs was channelled and conducted to a lagoon on the southern part of the Quiulacocha tailings impoundment. 3. Methods 3.1. Sampling and field methods The field campaign was carried out during the dry season 2003 (May to July). Water and solid sampling was undertaken focussing on the element output of the waste rock dump. A total of 68 mineral and rock samples at 53 sampling points and 4 water samples at 4 sampling points were taken from the surface of the Excelsior waste rock dump (Fig. 1B). The mainly vertical water pathway suggested an element transport from the top to the base. Therefore, solid samples were classified as: (1) altered rock samples from the surface of the top terraces (altered primary minerals with a lower amount of mainly in situ-formed secondary mineral), termed AR top samples in this study; (2) altered rock samples from the base of the Excelsior waste rock dump, termed AR base samples (Fig. 3); (3) precipitated secondary mineral samples (efflorescent salts) from the surface of the top terraces, termed ES top samples and (4) precipitated secondary mineral samples (efflorescent salts) from the base, termed ES base samples (Fig. 3, centre). 3.1.1. Water sampling At water sampling points, temperature, pH (WTW pH meter), Eh (WTW Eh meter) and electrical conductivity were measured immediately on-site. The samples were filtered through a 0.2 m cellulose membrane filter and split into two sub-samples. One was acidified to pH b 2 with HNO3 for cation analysis. The second untreated sample was stored b 4 C for anion analysis. 3.1.2. Solid sampling Solid sampling points were described in the field by rock type, alteration degree and, if possible, a description and identification of mineral content. The paste pH of the

sample was taken according to MEND (1991) with a WTW pH meter. Samples were air-dried (b 35 C) and homogenised by crushing/grounding with an agate mill. Humid ES samples were sealed in PET-sampling bottles directly on-site to prevent the alteration of minerals. 3.2. Geochemical methods 3.2.1. X-ray fluorescence spectroscopy For trace element analysis of solids, aliquots (4 g) of 78 samples were dried at 105 C, ground with an agate ball mill (Retsch), mixed with Hoechst wax, pressed to pellets and analysed using energy-dispersive X-ray fluorescence (EDXRF). The measurements were performed with the XRF-spectrometer XLAB 2000 (SPECTRO Instruments) running the software package X-LAB Pro 2.2. The calibration of the spectrometer was based on certified and measured data of about 50 reference materials including iron-rich soils, river and lake sediments and geological materials. In cases in which the analysed samples were strongly enriched with heavy metals (e.g. Fe, Cu, Zn and Pb), the sample material was diluted with SiO2 powder (Riedel-deHaen) to adjust the metal concentration to within the working ranges of the available calibration. For major element analysis, a further part of the sample powder was diluted with (Li2B4O7) (1 g sample + 7 g (Li2B4O7)) to prepare glass discs produced by fusion. The measurements were performed using the wavelength dispersive X-ray fluorescence (WDXRF) spectrometer S4 Pioneer (Bruker-axs), equipped with a 4 kW Rhodium X-ray tube. The spectrometer was operated in vacuum conditions and the 34 mm collimator mask was utilised in conjunction with the analysing crystals OVO55, Ge, LIF100 and LIF110. The calibrations of the WDXRF spectrometer for the major elements were adjusted by certified reference materials, CANMET-LKSD1-LKSD4 (lake sediments), CANMET-STSD1-STSD4 and GBW07309-11 (stream sediments), NIST-SRM2689 and NIST-SRM2691 (coal fly ashes) using the software package SPECTRAplus. 3.2.2. Leach tests and water analysis The German standard method DIN38414 (1984) was used to analyse the solubility of waste rock minerals in water. The chemical properties of the leachates and the water-soluble fraction from solid samples from the upper terraces and the base of the Excelsior waste rock dump were compared to analyse enrichment and fixation of elements. From the base of Excelsior waste rock dump, 9 AR samples with similar distances between the sampling

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points were chosen. From the top of the Excelsior waste rock dump, 10 AR samples were chosen. From each sample, pre-dried (b 35 C) and milled aliquots of 10 g were mixed with 100 ml of deionised water (pH 7, Eh of 0.45 V, not buffered) and shaken for 24 h at 100 rpm. The leachates were filtered through 0.2 m cellulose nitrate filters. The conductivity and pH of the leachates were measured immediately. The leached solid samples were dried (b35 C) and weighed to calculate the percentage of soluble phases. Major elements of leachates and water samples from the Excelsior waste rock dump were analysed using ion chromatography (Dionex DX-120). Trace elements were analysed using ICPMS (Hewlett-Packard 4500, Institute F.-A. Forel, University of Geneva, Switzerland) and ICPAES (Spectro Spectroflame P/M, UFZ Umweltforschungszentrum, Leipzig, Germany). Leach tests for 9 ES samples (5 samples from the upper terrace, 4 samples from the base of the Excelsior waste rock dump) were performed to confirm the high water-solubility of pure efflorescent salt samples (water soluble fraction between 89.2 and 94.4 wt.%). Due to their high water-solubility, XRF data of ES samples were used instead of leach test data for the above mentioned analysis of element enrichment and fixation. 3.3. Mineralogical methods 3.3.1. Optical microscopy Polished sections and polished thin sections of selected bulk samples were prepared using epoxy resin to embed the loose-packed samples and analysed using transmitted light and reflected light microscopy. 3.3.2. X-ray diffraction analysis All samples were analysed as bulk samples with the aid of X-ray diffraction (XRD), using a Siemens D5000 diffractometer equipped with monochromated CuK ( = 1.54056 ) X-radiation. Conserved humid ES samples were grounded with an agate mortar and analysed immediately to prevent the alteration of minerals, e.g. by the loss of crystal water. Scan settings were 0.05 2 step size and 2 s counting time per step. Peak interpretation was performed using the program suite DIFFRAC AT. 3.3.3. Differential X-ray diffraction analyses The poorly crystalline Fe(III) hydroxide schwertmannite was detected in a two-step sequential extraction procedure and differential X-ray diffraction (DXRD) as described by Dold (2003). The diffractometer settings were 0.05 2 step size and 20 s counting time per step.

The milled samples were treated in the first step with distilled water for 1 h and in the second step in darkness with 0.2 M ammonium oxalate at pH 3, for 15 min (after Dold, 2003). Scans were done before and after each treatment step. Scans from the ammonium oxalatetreated samples were intensity-corrected and then subtracted from the scans of the water-treated samples. The leachates from the sequential extraction were filtered (0.2 m) and analysed for element concentrations as described in Leach tests and water analysis (3.2.2). 4. Results 4.1. Mineralogy At the Excelsior waste rock dump, three different types of waste rocks were found (Table 1): (1) sulfiderich rocks from the quartzpyrite ore body and its Fe (III)-oxide-rich oxidation products near the surface, (2) sericitised monzonites/tuff and (3) dolomitic rocks from the host rock formation. These rocks were characterised by their different contents of acid-producing/acid-consuming minerals and their different degree of alteration. 4.1.1. Quartzpyrite rocks The main waste rock at the Excelsior waste rock dump belonged to the quartzpyrite body. Quartz and pyrite as major phases dominated the mineral

Table 1 AMD-relevant characteristics of rock types at the Excelsior waste rock dump Rock type Volume share AMD-neutral primary minerals Acid-producing primary minerals Alteration degree (estimated in field) Acid-consuming primary minerals Liberated elements (major fraction) Liberated elements (minor fraction) Secondary minerals Quartzpyrite rocks 7080% Quartz, hematite Pyrite Low (b10%) Not present Volcanic rocks 1520% Quartz, muscovite Pyrite Very high (N90%) Albite Carbonatic rocks ca. 5% Quartz Not present High (N50%) Dolomite Ca, Mg

Fe, Zn, Cu, Mn, S Fe, S Pb, As, Cd Gypsum, jarosite, plumbojarosite, hydronium jarosite, metal sulfates, Fe(III) hydroxides K, Ca

Hydronium Gypsum, Mg jarosite, sulfates jarosite, kaolinite, Fe sulfates, Fe(III) hydroxides

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assemblage in AR samples. The ore minerals sphalerite, tennantite, cerussite, galena and coronadite were identified as minor and trace phases and anglesite as a primary and possibly secondary trace mineral in the Excelsior waste rock dump. A different alteration intensity of small pyrite grains (up to 2 mm) was observed in thin sections. Intact, idiomorphic pyrite crystals were found in close proximity to strongly altered pyrite. Pyrite grains greater than 2 mm showed alteration rims of varying thickness (up to 1.5 mm) consisting of microcrystalline Fe(III) hydroxides. Massive pyrite rocks in the field showed superficial alteration with alteration rims of less than 1 mm. Due to the observed oxidation grades, a long-term AMD potential by the pyrite content must be assumed. A minor fraction of waste rocks from the quartzpyrite body belonged to the oxidized top of the quartzpyrite body in situ at the deposit. Rocks from this gossan contain quartz and hematite/goetite as major phases. 4.1.2. Volcanic rocks Volcanic rocks (quartz monzonite/tuff) in contact with the ore body could originally contain up to 15 vol.% pyrite in disseminated distribution due to the sericitic alteration during the sulfide deposition (personal communication, Volcan geologists). This contributed a further important quantity of pyrite to the system in addition to the pyrite from the ore body. Pyrite crystals in volcanic rocks are small in size (b 1 mm), the rock matrix has a high porosity. At the Excelsior waste rock dump volcanic rocks were observed to be already strongly altered. Boulders of volcanic rocks of up to 1 m in diameter had already completely decomposed into white, loose material with grain sizes of several mm and a strongly acidic paste pH (1.312.58, n = 6). Microscopic and XRD studies showed that the main primary mineral fractions of these rocks were quartz (20 vol.%) and altered relicts of albite (NaAlSi3O8) ( 5 vol.%). Agglomerates of secondary minerals (microcrystalline Fe(III) hydroxides, muscovite, kaolinite and gypsum) made up the major fraction (N 70 vol.%). From the original pyrite content, only relicts remained, contributing less than 1 vol.% of the total volcanic rock mineral assemblage. These observations pointed to the interpretation that due to the small crystal size and the high rock porosity, pyrite in the volcanic rocks oxidized much faster than massive pyrite from the quartzpyrite body. This resulted locally in strongly acidic environment where volcanic rocks were deposited. AMD from these areas was suggested to accelerate the further alteration of other waste rocks in the waste rock dump.

4.1.3. Carbonatic host rocks Less than 5 wt.% of the waste rocks belonged to the host rock formation and contained quartz, dolomite and siderite as major mineral phases. While dolomite can neutralize protons, siderite may additionally produce protons through the hydrolysis of liberated Fe(III), which can oxidize pyrite. This fact reduces the neutralization capacity of this type of carbonatic waste rocks. At the surface of the Excelsior waste rock dump, dolomite was still present at some sites. This suggested that rain infiltrated rapidly into the Excelsior waste rock dump and that acid solution could not migrate horizontally on the surface. Inside the Excelsior waste rock dump, carbonates were assumed to be mostly dissolved due to acid pore water. The generally low proportion of carbonatic rocks on the waste rock assemblage and the mix of acid-consuming and acidproducing carbonates in this rock type indicated that the Excelsior waste rock dump has an extremely low acid neutralization capacity. This led to an acidic environment with an average paste pH of 2.8. The pH depended strongly on the presence of dolomite; values varied between pH 0.8 and 4.7 for waste rock areas without dolomite (48 sampling points) and between pH 5.1 and 7.3 for areas with dolomite (6 sampling points). 4.1.4. Low soluble secondary minerals Solid solutions of secondary hydronium jarosite ((H3O)Fe3(SO4)2(OH)6) and K-jarosite (KFe3(SO4)2 (OH)6) were observed in most AR samples. The X-ray patterns of solid solutions of alkali jarosites as pointed out by Dutrizac and Jambor (2000) are very similar to the X-ray pattern of hydronium jarosite ((H3O)Fe(SO4)2 (OH)6). However, the small amounts of feldspars and other alkali-bearing minerals in the Excelsior waste rock dump resulted in a low availability, especially of Na, and were likely to favour the formation of hydronium jarosite instead of the thermodynamically more favoured solid solution of alkali jarosites. The XRD identification of hydronium jarosite also in samples with Na concentrations below detection limit supported this interpretation. In samples rich in Pb, the XRD interpretations suggested the presence of solid solutions between jarosite, hydronium jarosite and plumbojarosite (PbFe6(SO4)4(OH)12), possibly associated with beudantite (PbFe3(AsO4)(SO4)(OH)6). Goethite as a minor phase was found in samples with the typical altered rockmineral association pyrite (hydronium/plumbo) jarositegypsum. Some AR samples were collected at superficial water pathways. These samples were characterised by small grain sizes (b 1 mm), quartz as the major primary

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Table 2 Major secondary Fe-, Mg-, Zn- and Pb-sulfates of the Excelsior waste rock dump Fe-sulfates Melanterite (FeSO47H2O) Siderolite (FeSO45H2O) Fibroferrit (Fe(SO4) (OH)5H2O) Rozenite (FeSO44H2O) Szomolnokite (FeSO4H2O) Romerite (Fe3 (SO4)414H2O) Copiapite (FeFe4 (SO4)6(OH)220H2O) Mg-sulfates Epsomite (MgSO47H2O) Starkeyite (MgSO44H2O) Kieserite (MgSO4H2O) Zn-sulfates Pbsulfates

Goslarite Anglesite (ZnSO47H2O) (PbSO4) Gunningite (ZnSO42H2O) Changoite (Na2Zn (SO4)24H2O)

marginal intergrowth with microcrystalline Fe(III) hydroxides, and (2) very small idiomorphic crystals at the boundary to submicroscopical size, possibly resulting from fresh precipitation from pore water and/or as result of precipitation during the drying process after sampling. 4.2. Geochemical results 4.2.1. Solid sample analyses 4.2.1.1. Major elements. Si, Fe and S from the quartz pyrite body dominated the element composition of the AR samples average concentrations (Table 3) with average concentrations of 28.2 10.5 wt.% SiO2 in AR top samples/32.5 15.0 wt.% SiO2 in AR base samples, 27.0 9.5 wt.% Fe2O3 in AR top samples/22.4 12.1 wt.% Fe2O3 in AR base samples, 7.44 2.81 wt.% S in AR top samples/6.83 4.48 wt.% S in AR base samples. The volcanic rocks also contribute to these elements. Fe and S are the major elements in the ES samples (average concentrations: 21.5 5.9 wt.% Fe2O3 in top samples/18.8 12.4 wt.% Fe2O3 in base samples, 12.0 1.3 wt.% S in top samples/11.4 2.6 wt.% S in base samples). Fe and S concentrations were slightly higher in top samples than in base samples, while Si concentrations showed an opposite trend. These trends resulted probably from the flooring of the top terraces with pyriterich rocks. Aluminium in AR samples had its origin mainly in muscovite from altered volcanic rocks. A significant Al concentration in ES samples is only found in impure samples with high primary mineral content. This
Table 3 XRF data from AR and ES samples from the upper terraces (top) and from the base (base) of the Excelsior waste rock dump: average concentrations standard deviation of selected major and trace elements Element Na2O (wt.%) K2O (wt.%) CaO (wt.%) Al2O3 (wt.%) SiO2 (wt.%) MgO (wt.%) Mn (wt.%) Fe2O3 (wt.%) S (wt.%) Cu (wt.%) Zn (wt.%) Pb (wt.%) Cd (mg/kg) As (mg/kg) AR (top) (n = 17) 0.15 0.15 1.41 0.78 1.94 4.23 6.23 2.60 28.16 10.45 0.67 0.34 0.23 0.23 26.95 9.47 7.44 2.81 0.11 0.21 0.87 0.57 1.10 0.82 23 15 2030 1433 AR (base) (n = 32) 0.30 0.32 1.40 1.92 4.86 4.62 5.93 4.44 32.51 15.00 1.53 1.96 0.65 0.74 22.38 12.09 6.83 4.48 0.08 0.20 1.19 1.13 1.14 2.28 48 83 1205 1052 ES (top) (n = 5) 0.49 0.28 0.18 0.40 0.35 0.41 1.09 1.53 2.81 4.53 2.02 1.33 1.14 0.59 21.48 5.92 11.99 1.25 1.27 2.36 2.94 1.31 0.10 0.22 77 62 896 561 ES (base) (n = 12) 0.62 0.46 0.27 0.38 3.69 5.98 0.92 0.84 3.77 4.23 2.57 1.98 2.73 3.05 18.79 12.44 11.38 2.45 0.81 2.79 3.40 2.90 0.13 0.18 80 88 2043 3694

mineral fraction and a high content of secondary Fe(III) hydroxides (up to 60 vol.%). Fe(III) hydroxides appeared as light yellow to dark brownish agglomerates. A clear identification for these samples by XRD was not possible. One sample from the top of the waste rock dump (CPE-61(AR), Fig. 1B) and one from the base of the waste rock dump (CPE-32(AR)), both with a high content of poorly crystalline Fe(III) hydroxides, were selected for DXRD analyses. In both samples, schwertmannite (Fe16O16(OH)12(SO4)2) was identified as main secondary Fe-mineral. 4.1.5. Water-soluble secondary minerals Gypsum, Mg-sulfates and heavy metal sulfates were the major phases in ES samples. This mineral group represented the water-soluble efflorescent salts precipitated from oversaturated pore solutions. The most frequent metal sulfates (Table 2) were Fe-sulfates (melanterite, rozenite, less frequently romerite, siderolite, copiapite, szomolnokite and fibroferrite) followed by Mg-sulfates (epsomite, starkeyite and kieserite). In addition to these minerals, Zn-sulfates (goslarite, gunningite, changoite) and Mn-sulfates (mallardite, MnSO47H2O) could be found at some sites. Cu concentrations reached up to 10 wt.% in ES samples. An identification of Cu-minerals by means of XRD or optical microscopy was not possible. This suggested that Cu was not precipitated as a Cu-mineral but substituted metals in other sulfates (mainly melanterite) as also described from other sites (Jambor et al., 2000). Two different types of gypsum appeared: (1) crystals of between 0.05 and 0.4 mm with irregular shapes and

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suggested that high Al contents were mainly related to primary silicates. The concentrations for Na and K in AR samples were low due to the low content of primary Na and K-minerals in the primary mineral assemblage (average concentrations: 0.15 0.15 wt.% Na2O for AR top samples/0.30 0.32 wt.% Na2O for AR base samples; 1.41 0.78 wt.% K2O for AR top samples/ 1.40 1.42 wt.% K2O for AR base samples). While Na was enriched in ES samples (0.49 0.28 wt.% Na2O for ES top samples/0.62 0.46 wt.% Na2O for ES base samples), K showed a contrary trend (0.18 0.40 wt.% K2O for ES top samples/0.27 0.38 wt.% K2O for ES base samples). This suggested that K was stronger fixed in the system, probably due to the formation of K-jarosite. Ca and Mg from the dolomitic ore host rock had lower average concentrations in AR samples from the upper terraces (1.94 4.23 wt.% CaO in top samples/ 4.86 4.62 wt.% CaO in base samples, 0.67 0.34 wt.% MgO in top samples/1.53 1.96 wt.% in base samples). The reason for this observation was also the flooring of the top terraces with pyrite-rich, Ca-/Mg-mineral-poor rocks. Ca is not enriched in ES samples while Mg showed enrichment (average concentrations: 0.35 0.41 wt.% CaO in top samples/3.69 5.98 wt.% CaO in base samples, 2.02 1.33 wt.% MgO in top samples/ 2.57 1.98 wt.% MgO in base samples). 4.2.2. Heavy metals and arsenic 4.2.2.1. Copper, zinc and cadmium. AR samples contained a higher average Cu concentration in top samples (0.11 0.21 wt.% Cu) than in base samples (0.08 0.20 wt.% Cu) due to enargitetennantite veins in the quartzpyrite body (Einaudi, 1977) and the flooring of the terraces with pyrite-rich rocks. Cu is enriched in ES samples (average concentrations of 1.27 2.36 wt.% in top samples/0.81 2.79 wt.% in base samples). The primary mineral assemblage of the waste dump displayed a high average concentration of Zn (0.87 0.57 wt.% for AR top samples/1.19 1.13 wt.% for AR base samples), due to the main Zn minerals sphalerite (ZnS) and marmatite ((Zn,Fe)S) from the ore body. In ES samples, Zn was enriched in the form of efflorescent salts (averages: 2.94 1.31 wt.% Zn in top samples/3.40 2.90 wt.% Zn in base samples). Especially at overhangs which formed a protection against rain at the base of Excelsior waste rock dump, maximum Zn concentrations (up to 8.5 wt.% Zn, sample CPE-31(ES)) were found. Cadmium occurred as a substitute in sulfide minerals of the ore body (e.g. in sample CPE-2(AR) with 15 wt.% sphalerite, 295 mg/kg Cd; and CPE-12(AR)

with 10 wt.% tennantite ((Cu,Fe)12As4S13), 381 mg/kg Cd). The average Cd concentrations in the ES samples showed enrichment (77 62 mg/kg Cd for top samples/ 80 88 mg/kg Cd for base samples) in comparison to the AR samples (averages: 48 83 mg/kg Cd in top samples/23 15 mg/kg Cd in base samples). Cadmium was suggested to be incorporated into or coprecipitated with metal sulfates (e.g. in the sample CPE-30b(ES) with rozenite, starkeyite and 300 mg/kg Cd; sample CPE-52(ES) with szomolnokite and 192 mg/kg Cd), as described from other sites (Alpers et al., 1994). 4.2.2.2. Lead. The sulfide ore mineral galena PbS and its alteration product anglesite (PbSO4) (as primary mineral and also as freshly formed secondary mineral) represented the lead content in the Excelsior waste rock dump (average of 1.10 0.82 wt.% Pb for AR top samples/1.14 2.28 wt.% Pb for AR base samples). In the zones where secondary efflorescent salts particularly precipitated (mainly at the base of the waste rock dump), the average Pb concentration was nearly one tenth of that in the AR samples (average of 0.10 0.22 wt.% Pb for ES top samples/0.13 0.18 wt.% Pb for ES base samples). The low concentration of Pb in the ES samples pointed to the low solubility of the mineral anglesite and the low mobility of Pb in the sulfate-rich Excelsior waste rock dump environment. 4.2.3. Arsenic Sources for arsenic at the Excelsior waste rock dump were mainly the arsenic-rich pyrite, arsenopyrite (FeAsS) and enargite (Cu3AsS4)/luzonite (Cu3AsS4) from the ore body, but also realgar (As4S4) and orpiment (As2S3), which were part of the supergene mineral assemblage of the Cerro de Pasco mine (Einaudi, 1977).
Table 4 Heavy metal and arsenic concentrations (ICPMS) of sequential extractions for the Fe(III) hydroxides Type sample As Cd Cu Fe Mn Pb Zn (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) 0.02 0.02 0.31 0.02 84.5 2.6 45.72 11.21 0.003 0.009 32.52 8.20

Water leach CPE-32 0.26 (AR) CPE-61 b0.06 (AR)

NH4-ox. AC leach CPE-32 73.74 b0.01 (AR) CPE-61 b0.06 b0.01 (AR)

0.12 0.02

803 922

0.26 0.22

0.044 0.005

0.73 0.45

Sampling locations: see in Fig. 1B.

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AR samples displayed higher average concentrations in top samples (2030 1433 mg/kg As) than in base samples (1205 1052 mg/kg As) due to the flooring of top terraces with pyrite-rich rocks. Sequential extraction of an Fe(III) hydroxide-rich AR sample from the base of the Excelsior waste rock dump (CPE-32(AR)) showed a high concentration for As (up to 73.7 mg/L) in the Fe(III) hydroxide leach step (Table 4). This confirmed the known sorption capacity of Fe(III) hydroxides for As (Dold and Fontbot, 2001; Fukushi et al., 2003; Lebrun et al., 2004). In a second AR sample (CPE-61(AR)) from the top terrace of the Excelsior waste rock dump, schwertmannite was also identified. In contrast to the first mentioned sample, this sample contained a low concentration of As in the Fe(III) hydroxide leach step

(b0.06 mg/L). The low As concentration most probably resulted from As-poor sulfides in this sampled area. ES samples displayed a high average concentration of arsenic and enrichment at the base of the Excelsior waste rock dump (averages: 896 561 mg/kg As for ES top samples/2043 3694 mg/kg As for ES base samples), suggesting that mobile arsenic can be fixed when metal sulfates precipitate, as observed at other waste rock dumps (Gier et al., 2003). 4.2.4. Water leach tests After 24 h of stirring, all leachates possessed acidic pH values varying between 1.2 and 5.6 for the AR samples (Table 5). The water-soluble fraction of the leached AR samples represented between 2.6 and 39.6 wt.% and led in

Table 5 Water analyses of leachates from AR sample and AMD water samples: pH, Eh, electrical conductivity (EC), pH, ICPMS data and soluble fraction (SF)/total dissolved solids (TDS) of selected elements; average and standard deviation of the different sample categories Type/ Sample Leachates AR (top) CPE-44 CPE-48 CPE-49 CPE-50 CPE-54 CPE-55 CPE-56 CPE-57 CPE-59 CPE-62 Average S.D. AR (base) CPE-2 CPE-7 CPE-11 CPE-15 CPE-18 CPE-24 CPE-28 CPE-30 CPE-35 Average S.D. All leachates Average S.D. AMD water CPE-W1 CPE-W2 CPE-W3 CPE-W4 pH EC As Ca Cd Cu Fe K Mg Mn Na Pb S Zn SF Eh (mV) (mS/cm) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (wt.%)

2.43 1.20 2.56 2.32 2.33 2.17 2.74 2.32 2.33 2.32 2.27 0.41 4.02 5.60 3.79 2.82 5.47 2.88 2.91 2.77 3.20 3.72 1.12 2.96 1.09 4.86 4.94 5.10 2.78

n.m. n.m. n.m. n.m. n.m. n.m. n.m. n.m. n.m. n.m.

4.0 5.4 4.6 5.2 3.5 5.0 4.0 6.3 14.5 7.0 6.0 3.2 3.6 2.4 8.7 5.2 3.2 9.7 3.0 8.3 5.1 5.5 2.8 5.7 8.3

0.92 3.30 0.74 14.81 0.02 4.63 0.08 11.99 33.27 7.07 7.68 10.35 0.08 bdl bdl 0.10 bdl bdl 0.14 0.12 0.26 0.08 0.09 4.08 8.29 2.81 2.09 1.98 7.99

105 60 539 66 83 259 501 219 360 164 236 178 567 635 517 566 564 504 523 608 382 541 73 541 73 411 559 694 614

0.47 0.26 0.57 0.38 0.25 0.47 0.50 0.31 4.49 0.89 0.86 1.29 14.81 0.46 1.76 0.92 0.34 0.58 1.26 0.04 1.40 2.40 4.69 1.59 3.35 0.92 0.57 3.58 6.60

0.50 0.00 4.80 10.92 0.00 22.45 0.00 0.00 35.76 13.86 8.83 12.19 15.55 bdl 1.51 4.67 bdl 3.53 16.67 0.71 11.78 6.05 6.77 7.51 9.84 1.08 1.13 1.28 161.1

452 677 541 1225 157 872 49 1968 7400 1720 1506 2164 76 0.8 251 263 0.1 141 1452 44.9 350 286 454 928 1681 3685 3152 5640 1632

2.64 4.86 4.49 4.14 6.60 7.57 7.64 7.32 7.38 6.76 5.94 1.76 0.4 2.1 bdl bdl 3.6 bdl bdl 13.0 bdl 2.1 4.3 2.1 4.3 19.2 25.0 27.7 3.1

70 69 91 88 74 6 104 7 145 116 77 44 95 29 657 52 263 987 178 31 194 276 330 276 330 3158 3549 4716 7792

75.6 91.1 90.4 145.2 71.8 69.1 186.9 29.3 85.3 226.1 107.1 60.3 n.m. n.m. n.m. n.m. n.m. n.m. n.m. n.m. n.m.

7.24 6.90 8.15 6.98 8.61 6.28 7.80 11.58 5.43 8.36 7.73 1.67 1.2 0.8 0.9 bdl 3.1 0.5 bdl 0.8 bdl 0.8 1.0 0.8 1.0 73.8 121 8.2 bdl

0.06 1.85 0.03 0.02 0.05 0.16 0.11 0.28 0.08 0.03 0.27 0.56 2.27 0.35 0.07 0.14 bdl 0.06 0.22 0.06 bdl 0.35 0.73 0.31 0.63 1.17 0.55 1.28 0.14

917 167 1110 103 1620 152 1650 127 540 86 1250 130 720 146 1890 116 10660 1389 2468 290 2283 271 3000 397 1024 535 2110 1085 820 2074 1928 634 1139 1261 616 1261 617 8100 6820 9730 9800 447 107 708 322 68 491 611 18 521 366 250 315 330 1845 1218 2302 3000

6.3 9.8 5.9 21.3 5.9 8.4 7.4 14.1 39.6 13.2 13.2 10.5 27.4 2.6 12.7 5.4 4.6 13 3.3 11.8 6.4 9.7 7.8 11.5 9.2 TDS 4.7 5.6 5.2 7.5

n.m. n.m. n.m. n.m. n.m. n.m. n.m. n.m. n.m.

107 70 2258 1752 2467 2625

359 336 319 684

21.2 19.0 23.3 26.0

Abbreviations: top: samples from the surface of the upper terraces of the Excelsior waste rock dump; base: samples from the base of the Excelsior waste rock dump; S.D.: standard deviation; n.m.: not measured; bdl: below detection limit. Sampling locations: see Fig. 1B.

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high electrical conductivity in the leachates (between 2.4 and 14.5 mS/cm). All leachates showed high concentrations of heavy metals and also of Ca (average: 236 178 mg/L for AR top samples/541 73 mg/L for AR base samples), Mg (average: 77 44 mg/L for AR top samples/ 276 330 mg/L for AR base samples), As (average: 7.7 10.4 mg/L for AR top samples/0.08 0.09 mg/L for AR base samples) and S (average: 2283 3000 mg/L for AR top samples/1261 616 mg/L for AR base samples). The high concentrations of Ca and Mg represented the content of water-soluble secondary gypsum and Mg-sulfates (e.g. starkeyite, MgSO44H2O). The dissolution of Fe sulfates generated high Fe concentrations (average: 1506 2164 mg/L for AR top samples/286 454 mg/L for AR base samples) in the leachates. The liberated Fe(II) can be oxidized to form Fe(III) which is an effective sulfide oxidizer (Singer and Stumm, 1970). This process is supposed to enhance the sulfide oxidation at the Excelsior waste rock dump. The average concentrations of Cu and Zn in leachates were 8.8 12.2 mg/L for AR top samples/6.1 6.8 mg/L for AR base samples and 271 397 mg/L for AR top samples/366 250 mg/L for AR base samples, respectively. The high concentrations displayed clearly that Zn- and Cu-containing secondary sulfates dissolve rapidly in contact with water and liberate these metals. Pb showed low concentrations in the leachates (average 0.27 0.56 mg/L for AR top samples/0.35 0.73 mg/L for AR base samples) due to the already discussed low solubility of anglesite. The concentrations of arsenic in the leachates varied greatly between samples from different locations and showed lower concentration in base sample leachates (average: 7.7 10.4 mg/L for AR top samples/0.08 0.09 mg/L for AR base samples). Fixation of As on Fe(III) hydroxides lowered possibly the concentration of As in pore solutions at the base of the waste dump. At the top local low As concentrations seemed to result from low concentrations of As in the surrounding primary minerals, as shown by the Fe(III) hydroxide leach test. Samples with high arsenic concentrations in the leachates (up to 33.3 mg/ L, sample CPE-59(AR)) had a very low paste pH (1.11.7) in the field, suggesting a high pyrite oxidation in these zones. This oxidation process liberated As which was fixed in the sulfides and resulted in the observed high concentration of As in the leachates. The leachates had an average Cd concentration of 0.9 1.3 mg/L for AR top samples/2.4 4.7 mg/L for AR base samples. This observation confirmed the suggestion that Cd was enriched at the base of the Excelsior waste rock dump in water-soluble secondary minerals, as discussed with the XRF data from solid samples.

Element concentrations varied widely, demonstrating the different content and composition of water-soluble secondary minerals in the samples. 4.2.4.1. AMD from the Excelsior waste rock dump. AMD samples originated from the broad spring zone at the south-western base of the Excelsior waste rock dump (CPE-W1 to 3, Fig. 1B) and from a small water outcrop at the north-western base (CPE-W4). CPE-W1 to 3 were linked together as a broad spring zone at the most recent, southern part of the Excelsior waste rock dump base. AMD from this zone was characterized by an acid pH (range: 4.865.10), high electrical conductivity (range: 19.0 23.3 mS/cm), a slightly oxidizing environment (range Eh: 319359 mV) and a high charge of metals (Table 5). The total flow rate of this spring zone is estimated to be around 10 L/s. CPE-W4 is an isolated, small water outcrop at the north-western, oldest area of the Excelsior waste rock dump. The more acid pH (2.78), higher Eh (684 mV) and higher electrical conductivity (26.0 mS/cm) in comparison with the broad spring zone in the SW seemed to result from the longer exposition of the waste rocks in this area and the therefore more advanced oxidation of sulfides. The high concentration of Cu in the water sample CPE-W4 (161.1 mg/L) possibly resulted from the source rocks in this area: the oldest waste rocks from the historically first mined Cu-rich and surface-near ore of the Cerro de Pasco deposit. The trends of mineral solubility and element mobility from the leach tests were confirmed by the heavy metal concentrations in the AMD waters: Cu 1.11.3 mg/L at CPE-W1 to 3, 161.1 mg/L at W4, Zn 12182302 mg/L at W1 to 3, 3000 mg/L at W4, Fe 36855640 mg/L at W1 to 3, 1623 mg/L at W4, Cd 0.93.6 mg/L at W1 to 3, 6.6 mg/L at W4. The metal concentrations were higher in comparison with the average concentration of the AR leaching tests. This observation was explained by the high interaction of pore water with altered waste rocks during the slow infiltration. The AMD effluents also contained high concentrations of As (CPE-W1 to 3: 2.02.1 mg/L As, CPE-W4: 8.0 mg/L As). Arsenic appeared to be not completely retained by Fe(III) hydroxides during the flow path in the Excelsior waste rock dump, probably due to its high concentration. Manganese showed high concentrations in leachates (data only available for AR top sample leachates: average 107 60 mg/L Mn). The sequential extraction data of the water extraction step (Table 4, 11.245.7 mg/L Mn) and the water data (Table 5, 17522625 mg/L Mn) also displayed high concentrations of Mn. Source of

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Mn seemed to be the dissolution of Mn-sulfates (e.g. mallardite, Mn(SO4)7H2O). 5. Discussion The comparison of the XRF, XRD, leach test and AMD data was used to identify source rocks of AMD and trace back the transport of acids and heavy metals and their retention at the Excelsior waste rock dump in form of freshly precipitated secondary minerals at the Excelsior waste rock dump. The heavy metals Zn, Cd, Mn as well as the alkaline earth metals Ca and Mg showed higher concentrations in AR samples from the base of the Excelsior waste rock dump than from its top terraces. The leach tests and XRF data from ES samples confirmed that these metals were enriched in ES samples, especially at the base of the waste rock dump. This enrichment was explained by the transport of AMD from the top to the base of the waste rock dump, leaching of heavy metals inside of the waste rock dump by the acidic solutions and the subsequent precipitation of metal sulfides due to evaporation of outcropping AMD during the dry season. Cu concentrations were lower in AR samples and their leachates from the base of the Excelsior waste rock dump than from the top. In ES samples, Cu is enriched in comparison to AR samples. This suggested that in the dry season, secondary Cu-bearing sulfates precipitated close to sites with high Cu concentration in altering pyrite-rich primary rocks. Water-soluble Fe-sulfates were the most abundant heavy metal sulfates at the waste rock dump. AMD and all leachates had high Fe and S concentrations indicating high water-solubility of Fe-sulfates and mobility for iron and sulfate, when water as solvent and transport medium was available, e.g. during the rainy season. AR samples from the top had higher concentrations of Fe and S due to flooring with pyrite-rich waste rocks. Leachates from AR samples and ES samples from the top terraces also had higher concentrations of leachable Fe and S in comparison with base samples and their leachates. This suggested that water-soluble Fe-sulfates precipitated in the dry season near to the oxidizing Fe-sulfides and depended in their concentration on the local concentration of Fe-sulfides. A possible explication for the lower Fe concentrations in leachates from samples from the base of the waste rock dump was the precipitation of not water-soluble secondary minerals like schwertmannite and jarosite in this zone. The heavy metal Pb showed no trends of enrichment. Pb had in samples from the top and from the base similar

concentrations, most probably due to the low solubility of primary and secondary anglesite. Potassium concentrations in AR samples from top and base samples were nearly the same, while AR samples from the base had higher sodium concentrations than AR samples from the top. The higher content of albite-rich volcanic rocks at the base was suggested to be the source of the higher concentrations of Na. Altering volcanic rocks were most probably also the reason of Na enrichment in ES samples at the base of the Excelsior waste rock dump. High concentrations in AMD samples displayed that both alkali metals were mobile after the alteration of its source rocks. Na and K concentrations in leachates from AR base samples were much lower than in leachates from AR top samples. This observation suggested that at the base of the waste rock dump K and Na were at least partially fixed in freshly precipitated, water-insoluble secondary minerals, e.g. jarosites. The high arsenic concentration in AR samples from the top resulted from the flooring of top terraces with pyrite-rich, arsenic-containing waste rocks. The arsenic enrichment in ES samples from the base suggested transport of dissolved arsenic, while the lower concentrations in leachates from base samples contradicted the mobility of As. These observations and the high As concentrations in AMD waters at the base suggested that As was mobile and transported to the base after liberation by the oxidation of As-containing sulfides. During the evaporation of pore water at the base of the waste rock dump arsenic appeared to be fixed in minerals with low water-solubility, e.g. due to adsorption on freshly precipitated Fe(III) hydroxides. 6. Conclusion At the Excelsior waste rock dump, pyrite from two different sources (ore body/volcanic rocks) was present as an acid producer in a high concentration (estimated N60 wt.% of the total mineral assemblage). Ore sulfides (Zn, Pb) were found in local concentrations up to 10 wt.%. Minerals with a capacity of neutralising AMD were only minor or trace fractions (b5 wt.% carbonates). Sulfide oxidation took place producing a strongly acidic environment (average paste pH 2.8). Pyrite from the Cerro de Pasco quartzpyrite body (N 60 wt.% of the total mineral assemblage) oxidized slowly, producing a long-term risk of AMD. Pyrite from volcanic waste rocks represented ca. 1 wt.% of the total mineral assemblage of the Excelsior waste rock dump. This pyrite has due to small crystal size and high rock porosity a high oxidation rate and liberated acids and Fe(III) which could accelerate further pyrite oxidation. The

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Fig. 4. Model of climatic effects on the formation and dissolution of efflorescent salts and the transport and mobility of acid, metal-rich solutions at the Excelsior waste rock dump: (A) dry season; (B) rainy season.

current study allowed the development of a schematic model of the seasonal variation in secondary mineral formation and dissolution and subsequent element outflow from the Excelsior waste rock dump (Fig. 4). (A) High evaporation during dry seasons concentrated the acidic, metal-rich pore solutions near to the surface of the Excelsior waste rock dump up to supersaturation and caused the successive precipitation of efflorescent metal salts. The formation of secondary gypsum, Fe (III)-hydroxides, Fe-sulfates (partly Cu-bearing) and minor quantities of Mg-, Zn- and Mn-sulfates was observed. At the base of the Excelsior waste rock dump a major precipitation zone of efflorescent salts was found during the dry season as result of outcropping, evaporating pore solutions. (B) Rainwater dissolved during the wet season water-soluble secondary minerals precipitated during the dry period, infiltrated and transported acids and mobile elements into the waste rock dump where they react with primary minerals and leach heavy metals (Zn, Cu, Cd) out of primary sulfides. The heavy metals Fe, Mn, Zn, Cu, Cd (as cations), Ca 2 and Mg (as cations) and the anion SO4 were mobile in the Excelsior waste rock dump system. Arsenic was only partly retarded in the system by adsorption on Fe (III) hydroxides, AMD waters still contained up to 7.99 mg/L As. The mobility of Pb was limited by the low solubility of the Pb mineral anglesite. Most of the heavy metal sulfides precipitated during the dry season seemed to be dissolved during the wet season and left the Excelsior waste rock dump as AMD. As result, the formation of an enrichment of heavy metal as efflorescent salts at the base of the Excelsior waste rock dump was limited to the dry season. Two main pathways were assumed for the outcropping highly mineralized acid solutions: (1) outcrop at a broad

spring zone at the base of the waste rock dump where the AMD was channelled and conducted to a lagoon on the Quiulacocha tailings impoundment, and (2) infiltration from the waste rock dump into the underlying parts of the Quiulacocha tailings impoundment. Due to the high quantity of sulfides (N 60 wt.%) in and the low neutralization potential of the waste rocks (b5 wt.% carbonates) as well as the slow oxidation of the pyrite content, a long-term AMD potential for the Excelsior waste rock dump must be assumed. Acknowledgements We thank A. Cornejo and J. Rosa del Castillo (Centromin Peru) for their permission, access to their properties and also their interest and support. Special thanks are due to the management and geologists and all staff involved in this project from VOLCAN S.A.A. for their interest, the access to the properties, their logistic support and their collaboration, especially V. Gobitz, F. Grimaldo, L. Osorio and W. Hevedia. We thank P. Schreiter, P. Schreck, W. Schmitz and G. Kommichau, University of Leipzig, Germany, as well as H.-R. Pfeifer and L. Dufresne, University of Lausanne, Switzerland, for analytical support and helpful discussions. For the ICP MS analyses, we give many thanks to P.-Y. Favarger from the Institute F.-A. Forel, Geneva, Switzerland. We thank R. Wennrich (UFZ Leipzig-Halle, Germany) for his analytical support. For their support in Peru in the field work, sample preparation and analytical approaches, we also would like to thank R. Mucho and R. Paredes (INGEMMET Peru) and J. Torrejn (GEPASAC Peru). The project was supported by the German National Academic Foundation and the Swiss National Science Foundation.

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J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97110 abandoned arsenic mine dump. Applied Geochemistry 18, 12671278. Gier, R., Sidenko, N.V., Lazareva, E.V., 2003. The role of secondary minerals in controlling the migration of arsenic and metals from high-sulfide wastes (Berikul gold mine, Siberia). Applied Geochemistry 18, 13471359. Hammarstrom, J.M., Seal II, R.R., Meier, A.L., Kornfeld, J.M., 2005. Secondary sulfate minerals associated with acid drainage in the eastern U.S.: recycling of metal and acidity in surficial environments. Chemical Geology 215, 407432. Jambor, J.L., 1994. Mineralogy of sulfide-rich tailings and their oxidation products. In: Jambor, J.L., Blowes, D.W. (Eds.), Short Course Handbook on Environmental Geochemistry of Sulfide Mine Waste, vol. 22. Mineralogical Association of Canada, Nepean, pp. 59102. Jambor, J.L., Nordstrom, D.K., Alpers, C.N., 2000. Metal-sulfates salts from sulfate mineral oxidation. In: Alpers, C.N., Jambor, J.L., Nordstrom, D.K. (Eds.), Sulfate Minerals: Crystallography, Geochemistry, and Environmental Significance. Mineralogical Society of America, Washington, D.C., pp. 277301. Lebrun, S., Morin, G., Cassiot, C., Bruneel, O., Duquesne, K., Bonnefoy, V., Personne, J.C., Elbaz-Poulichet, F., Guyot, F., Calas, G., 2004. Mineralogy of AsFe precipitates in acid mine drainage: the role of acidophilic bacteria. Geophysical Research Abstracts 6. MEND, Mine Environment Neutral Drainage Program, 1991. Acid rock drainage prediction manual, report 1.16.1b. Ottawa, CANMET, Department of Natural Resources, Canada. Petersen, U., 1965. Regional geology and major ore deposits of central Peru. Economic Geology 60, 407476. Singer, P.C., Stumm, W., 1970. Acid mine drainage: the rate determinating step. Science 167, 11211123. Sracek, O., Choquette, M., Gelinas, P., Lefebvre, R., Nicholson, R.V., 2004. Geochemical characterization of acid mine drainage from a waste rock pile, Mine Doyon, Quebec, Canada. Journal of Contaminant Hydrology 69, 4571.

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